Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D201/00—Coating compositions based on unspecified macromolecular compounds
  • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
  • C09D201/06—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
  • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
  • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
  • C08G18/6225—Polymers of esters of acrylic or methacrylic acid
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D133/04—Homopolymers or copolymers of esters
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D133/04—Homopolymers or copolymers of esters
  • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C09D133/062—Copolymers with monomers not covered by C09D133/06
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D133/04—Homopolymers or copolymers of esters
  • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C09D133/062—Copolymers with monomers not covered by C09D133/06
  • C09D133/068—Copolymers with monomers not covered by C09D133/06 containing glycidyl groups
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
  • C09D143/04—Homopolymers or copolymers of monomers containing silicon
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2150/00—Compositions for coatings
  • C08G2150/20—Compositions for powder coatings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
  • C08L63/06—Triglycidylisocyanurates

Definitions

• the present invention relates to a novel thermosetting powder coating composition which is excellent in the finished appearance of coating film and in the blocking resistance.
• thermosetting powder coating compositions which are usable without a solvent have been increasingly used from the viewpoints of prevention of environmental pollution and conservation of environment.
• thermosetting powder coating compositions generally have a drawback of giving a coating film which is unsatisfactory in the finished appearance.
• the molecular weight of a vinyl copolymer used as the resin component of the composition has been lowered to reduce the viscosity of the coating composition thermally fused.
• the powder coating composition obtained in this way has posed a problem of being likely to cause blocking phenomenon that particles in the composition during storage weld together, thereby forming agglomerates.
• An object of the present invention is to provide a novel thermosetting powder coating composition free of the foregoing prior art drawback.
• Another object of the invention is to provide a novel thermosetting powder coating composition which is superior in any of the finished appearance of coating film and the blocking resistance.
• thermosetting powder coating composition comprising:
• a vinyl copolymer used as the resin component of the composition has generally a molecular weight distribution (represented by a weight average molecular weight/a number average molecular weight) of at least 2, namely too broad of a distribution. Therefore, when the molecular weight of a vinyl copolymer is lowered, the blocking phenomenon would tend to occur in the composition due to the low-molecular-weight compound.
• the inventors further researched based on the finding and discovered the following.
• the resulting powder coating composition is excellent in any of the finished appearance of coating film and the blocking resistance.
• the present invention has been completed based on these novel findings.
• the vinyl copolymer (A) used as the resin component in the composition of the present invention is 1,500 to 6,000 in number average molecular weight, 1.0 to 1.5, preferably 1.0 to 1.2, in molecular weight distribution as represented by a weight average molecular weight/a number average molecular weight and 40 to 100° C. in glass transition temperature, and contains at least one species of functional group selected from the class consisting of epoxy group, carboxyl group and hydroxyl group.
• a copolymer having a number average molecular weight of less than 1,500 tends to lower the blocking resistance of the composition and to impair the film properties such as mar resistance, weatherability, etc., whereas a copolymer higher than 6,000 in number average molecular weight tends to degrade the finished appearance of coating film. Hence the number average molecular weight outside said range is undesirable.
• the molecular weight distribution of the vinyl copolymer as represented by a weight average molecular weight/a number average molecular weight is above 1.5, it would be difficult to obtain a coating composition which is satisfactory in both the finished appearance of the coating film and the blocking resistance.
• the glass transition temperature of the copolymer is below 40° C., a lower blocking resistance is apt to result, whereas if it is above 100° C., the melt flowability would be lowered, thereby tending to degrade the finished appearance of coating film. Hence the glass transition temperature outside said range is undesirable.
• At least one species of functional group selected from the class consisting of epoxy group, carboxyl group and hydroxyl group in the copolymer is reacted with the curing agent to accomplish crosslinking.
• the vinyl copolymer may contain either only one species of these functional groups or a combination of at least two species of the functional groups, e.g. epoxy group and hydroxyl group, or carboxyl group and hydroxyl group.
• the copolymer has epoxy groups, it is desirable that the copolymer have an epoxy equivalent of about 280 to about 950.
• the copolymer with carboxyl groups has an acid value of about 30 to about 300 mg KOH/g.
• the copolymer with hydroxyl groups has a hydroxyl value of about 30 to about 300 mg KOH/g.
• the vinyl copolymer (A) can be prepared, for example, by living polymerization, particularly the living polymerization disclosed in Japanese Examined Patent Publication No.79685/1993, or by fractionating the copolymer produced by radical polymerization to give a specific molecular weight distribution.
• a copolymer is prepared by the living polymerization disclosed in Japanese Examined Patent Publication No.79685/1993, the living polymerization is performed using vinyl monomers, a polymerization initiator capable of forming an active species of a growing terminal, a co-catalyst and optionally a solvent and is terminated by inactivating the terminal with an active hydrogen source such as water, alcohol or the like, whereby the desired copolymer can be formed.
• an active hydrogen source such as water, alcohol or the like
• Examples of useful vinyl monomers are methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, glycidyl (meth)acrylate, allylglycidyl ether, 3,4-epoxycyclohexyl-methyl (meth)acrylate, trimethylsilyl (meth)acrylate, 2-(trimethylsiloxy)ethyl (meth)acrylate, etc.
• glycidyl (meth)acrylate In introducing epoxy groups into a copolymer, glycidyl (meth)acrylate, allylglycidyl ether, 3,4-epoxycyclohexyl (meth)acrylate or the like is used as the monomer.
• copolymerization is conducted using, for example, 2-(trimethylsiloxy)ethyl (meth)acrylate as the monomer, and then the group COOC 2 H 4 Si(CH 3 ) 3 in the side chain of the resulting copolymer is converted into a group COOC 2 H 4 OH by an alcohol.
• copolymerization is conducted using, for example, trimethylsilyl (meth)acrylate as the monomer, and then the group COOSi(CH 3 ) 3 in the side chain of the resulting copolymer is converted into a group COOH by an alcohol.
• Examples of useful polymerization initiators are (1-methoxy-2-methyl-1-propenyl)oxy!trimethylsilane, (2-methyl-1-propenylidene)bis(oxy)!bis trimethylsilane!, trialkylsilylnitrile, (2-methyl-1- 2-(trimethylsiloxy)-ethoxy!-1-propenyl)oxy!trimethylsilane, etc.
• Useful co-catalysts include, for example, tris(dimethylamino)sulfonium bifluoride, potassium ammonium bifluoride, boron trifluoride etherate, tetraalkyl ammonium bifluoride, tetrabutyl ammonium m-chlorobenzoic acid, tetraaryl phosphonium bifluoride, etc.
• the method of giving the specific molecular weight distribution to the vinyl copolymer (A) by fractionation of the copolymer prepared by radical polymerization is as follows.
• At least one species of monomer selected from the group consisting of an epoxy group-containing ethylenically unsaturated monomer, a hydroxyl-containing ethylenically unsaturated monomer and a carboxyl-containing ethylenically unsaturated monomer, and other radically polymerizable unsaturated monomer are polymerized in the presence of a radical polymerization initiator to give a copolymer.
• the obtained copolymer is usually a mixture of substances of various molecular weights having a molecular weight distribution of at least 2 as represented by a weight average molecular weight/a number average molecular weight.
• the copolymer is fractionated to give a molecular weight distribution of 1.0 to 1.5 by removing the low-molecular-weight substances and high-molecular-weight substances based on the difference of physical or chemical properties between the substances.
• Fractionation methods include conventional fractionation methods, for example, a method of fractionation utilizing a phenomenon that when an interaction is varied between the polymer and the solvent by altering the temperature of the polymer solution or the make-up of the solvent, the polymer solution achieves a phase separation into a thick solution and a dilute solution; ultracentrifuge for fractionation according to the degree of sedimentation variable with molecular weights; and molecular sieve method wherein high molecular weight gel particles of three-dimensionally reticulated structure or porous glass spheres are packed into a column and specimens are passed therethrough to achieve fractionation due to a difference in molecular size.
• epoxy group-containing ethylenically unsaturated monomers to be used in said radical polymerization are glycidyl (meth)acrylate, allylglycidyl ether, 3,4-epoxycyclohexylmethyl (meth)acrylate, etc.
• Useful hydroxyl-containing ethylenically unsaturated monomers include, for example, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, etc.
• Useful carboxyl-containing ethylenically unsaturated monomers include, for example, (meth)acrylic acid, maleic acid, etc.
• alkyl esters or cycloalkyl esters of (meth)acrylic acids such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-octyl (meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate and stearyl (meth)acrylate; alkoxyalkyl esters of (meth)acrylic acids such as methoxybutyl (meth)acrylate, methoxyethyl (meth)acrylate and ethoxybut
• radical polymerization initiators which can be used herein are benzoyl peroxide, di-tert-butylhydroperoxide, azobisdimethyl valeronitrile, azobisisobutyronitrile, etc.
• the curing agent (B) to be incorporated into the composition of the invention is a compound which achieves crosslinking by reaction with the epoxy groups, carboxyl groups or hydroxyl groups in the vinyl copolymer (A).
• curing agent for epoxy groups are, for example, polycarboxylic acids such as adipic acid, azelaic acid, sebacic acid, dodecanoic diacid and eicosanoic diacid, and polycarboxylic anhydrides prepared by dehydration condensation of at least one of these polycarboxylic acids.
• polycarboxylic acids such as adipic acid, azelaic acid, sebacic acid, dodecanoic diacid and eicosanoic diacid
• polycarboxylic anhydrides prepared by dehydration condensation of at least one of these polycarboxylic acids.
• curing agent for carboxyl groups are, for example, triglycidyl isocyanurate and like polyepoxides, and (bis(N,N')-dihydroxyethyl)adibamide (such as "Primid XL-552", product of Rohm & Haas Co., trade name) and like ⁇ -hydroxyalkylamides.
• curing agent for hydroxyl groups are, for example, ⁇ -caprolactam block products of isophorone diisocyanate (e.g., "Vestagon B-1530", Dicel Hules Co., trade name) and like blocked polyisocyanates, tetramethoxymethyl glycollyl (e.g. "Powderlink 1174", product of Mitsui Cyanamide Co., Ltd., trade name) and like polyalkoxy compounds.
• isophorone diisocyanate e.g., "Vestagon B-1530", Dicel Hules Co., trade name
• tetramethoxymethyl glycollyl e.g. "Powderlink 1174", product of Mitsui Cyanamide Co., Ltd., trade name
• the proportions of the components (A) and (B) in the coating composition of the invention are about 60 to about 92% by weight of the component (A) and about 8 to about 40% by weight of the component (B), based on the combined amount of the two components.
• the coating composition of the invention may contain, when required, additives in addition to the components (A) and (B).
• additives are organic coloring pigments such as quinacridone and like quinacridone pigments, pigment red and like azo pigments, Phthalocyanine Blue, Phthalocyanine Green and like phthalocyanine pigments, inorganic coloring pigments such as titanium oxide, carbon black and graphite, extender pigments such as calcium carbonate, barium sulfate, clay, talc and silica, metallic pigments such as micaceous iron oxide and aluminum flake, corrosion-resistant pigments such as red oxide, strontium chromate and zinc phosphate, curing catalysts such as dibutyltin diacetate, dibutyltin dioctate, dibutyltin dilaurate, triethylamine and diethanolamine, UV absorbers such as benzophenone compounds, benzotriazole compounds, salicylate compounds and oxalic acid anilide compounds, UV stabilizers such
• the coating composition of the invention can be prepared by fusing, kneading, cooling and pulverizing the vinyl copolymer (A), the curing agent (B), and optionally additives. It is suitable that the obtained powder have an average particle size of about 20 to about 100 ⁇ m.
• the coating composition of the invention is not particularly limited in applications and can be suitably used as a topcoat composition.
• Suitable substrates which are coated with the composition of the invention are those made of metals such as iron, steel, aluminum and zinc, alloys thereof or the like, those treated with zinc phosphate, iron phosphate or the like for chemical conversion and those coated with an undercoat and/or an intercoat.
• the coating composition of the invention is suitably applied to the substrate usually by electro-static powder coating method.
• a proper thickness of coating film when cured is about 10 to about 200 ⁇ m.
• the curing is carried out by heating the composition at a temperature of about 130 to about 200° C. for about 20 to about 60 minutes.
• the powder coating composition of the invention shows a remarkable effect of being superior in any of the finished appearance of coating film and the blocking resistance due to the use of the specific vinyl copolymer of the invention as the resin component of the composition.
• the copolymer a had a glass transition temperature of 68° C. and an epoxy equivalent of 406.
• the copolymer a was 2,590 in weight average molecular weight (Mw), 2,280 in number average molecular weight (Mn) and 1.13 in Mw/Mn.
• the trimethylsilyl methacrylate (440 g) was converted with methanol and corresponded to 239 g of methacrylic acid.
• the copolymer b had a glass transition temperature of 79° C. and an acid value of 196 mg KOH/g.
• the copolymer b was 2,690 in weight average molecular weight (Mw), 2,380 in number average molecular weight (Mn) and 1.13 in Mw/Mn.
• the trimethylsiloxyethyl methacrylate (456 g) a was converted with methanol and corresponded to 318 g of hydroxyethyl methacrylate.
• the copolymer c had a glass transition temperature of 71° C. and a hydroxyl value of 159 mg KOH/g.
• the copolymer c was 2,500 in weight average molecular weight (Mw), 2,240 in number average molecular weight (Mn) and 1.12 in Mw/Mn.
• a 600 g quantity of toluene was charged into a conventional reaction vessel equipped with a stirrer, thermometer, reflux condenser and the like, followed by heating and stirring.
• toluene started to be refluxed, 350 g of glycidyl methacrylate, 150 g of n-butyl methacrylate, 500 g of methyl methacrylate, and 40 g of azobisisobutyronitrile were added dropwise over a period of about 2 hours. After completion of addition, a reflux continued for a further 3 hours, and 10 g of azobisisobutyronitrile was added, followed by 1 hour's reflux. After termination of the reflux, the toluene was discharged outside the reaction vessel. When the temperature of the contents of the reaction vessel reached 150° C., the residual toluene was removed by vacuum distillation, and the residue was cooled, giving a solid epoxy group-containing vinyl copolymer d.
• the copolymer d had a glass transition temperature of 79° C. and an epoxy equivalent of 405.
• the copolymer d was 4,670 in weight average molecular weight (Mw), 2,310 in number average molecular weight (Mn) and 2.02 in Mw/Mn.
• the copolymer e had a glass transition temperature of 68° C. and an epoxy equivalent of 406.
• the copolymer e was 8,650 in weight average molecular weight (Mw), 3,040 in number average molecular weight (Mn) and 2.85 in Mw/Mn.
• the copolymer f had a glass transition temperature of 79° C. and an acid value of 196 mg KOH/g.
• the copolymer f was 4,820 in weight average molecular weight (Mw), 2,300 in number average molecular weight (Mn) and 2.10 in Mw/Mn.
• the copolymer g had a glass transition temperature of 71° C. and a hydroxyl value of 159 mg KOH/g.
• the copolymer g was 4,730 in weight average molecular weight (Mw), 2,350 in number average molecular weight (Mn) and 2.01 in Mw/Mn.
• Vinyl copolymers and curing agents used according to the make-up as shown in Table 1 were dry-blended at room temperature using a Henschel mixer. The blend of components was fused and kneaded in an extruder, cooled, finely divided by Pinding's mill and passed through a 150 mesh sieve, giving a powder coating composition according to the invention or a comparative powder coating composition.
• the curing agent (1) was a dodecanoic diacid
• the curing agent (2) was triglycidyl isocyanate
• the curing agent (3) was "Vestagon B-1530" (block polyisocyanate, product of Dicel Hules Co., trade name).
• Coating films were formed by a 2-coat 2-bake coating method as described below using as a clear topcoat composition the powder coating compositions prepared in Examples and Comparative Examples.
• An epoxy cationic electrodepositable coating composition was electrodeposited to a thickness of about 20 ⁇ m when cured on a dull steel panel of 0.8 mm thickness treated with zinc phosphate for chemical conversion, and was baked.
• "Magicron HM-22" product of Kansai Paint Co., Ltd., acryl-melamine metallic coating composition, trade name
• Each of said powder coating compositions was applied to the base coat by electrostatic coating to a thickness of about 70 ⁇ m when cured and was heated for curing at 160° C. for 30 minutes, giving a coating film.
• the powder coating compositions prepared above were checked for blocking resistance, finished appearance of cured coating and gloss thereof by the following methods.
• Blocking resistance of powder coating composition Each powder coating composition was placed into a cylindrical container having a bottom area of about 20 cm 2 to a height of 6 cm and left to stand at 30° C. for 7 days. Thereafter the composition was withdrawn and observed to check the condition for evaluation according to the following criteria. A: No agglomerate was found. B: Agglomerates like rice grains were found. C: Hardened into a mass in the shape of the container.
• Finished appearance of coating film The coating film was visually inspected and rated in the finished appearance according to the following criteria: A; Very good, B; Good, C; Impaired

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• 1995
  • 1995-07-24 US US08/765,460 patent/US5945487A/en not_active Expired - Fee Related
  • 1995-07-24 DE DE69514232T patent/DE69514232T2/de not_active Expired - Fee Related
  • 1995-07-24 EP EP95926018A patent/EP0773267B1/de not_active Revoked
  • 1995-07-24 WO PCT/JP1995/001469 patent/WO1996003464A1/ja not_active Application Discontinuation

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